WO2017100585A1 - Catalyseurs de métathèse d'oléfines - Google Patents

Catalyseurs de métathèse d'oléfines Download PDF

Info

Publication number
WO2017100585A1
WO2017100585A1 PCT/US2016/065844 US2016065844W WO2017100585A1 WO 2017100585 A1 WO2017100585 A1 WO 2017100585A1 US 2016065844 W US2016065844 W US 2016065844W WO 2017100585 A1 WO2017100585 A1 WO 2017100585A1
Authority
WO
WIPO (PCT)
Prior art keywords
optionally substituted
alkyl
aryl
hydrogen
cycloalkenyl
Prior art date
Application number
PCT/US2016/065844
Other languages
English (en)
Inventor
Adam M. Johns
T. Patric MONTGOMERY
Tonia S. AHMED
Robert H. Grubbs
Richard L. Pederson
Original Assignee
Materia, Inc.
California Institute Of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to EP24186768.8A priority Critical patent/EP4431180A2/fr
Priority to US16/060,466 priority patent/US10857530B2/en
Priority to PL16873924.1T priority patent/PL3386936T3/pl
Priority to CA3006976A priority patent/CA3006976A1/fr
Priority to EP16873924.1A priority patent/EP3386936B1/fr
Priority to JP2018530559A priority patent/JP6882295B2/ja
Application filed by Materia, Inc., California Institute Of Technology filed Critical Materia, Inc.
Priority to MX2018006987A priority patent/MX2018006987A/es
Priority to KR1020187019274A priority patent/KR20180116238A/ko
Priority to CN201680071920.XA priority patent/CN108368001B/zh
Publication of WO2017100585A1 publication Critical patent/WO2017100585A1/fr
Priority to IL259758A priority patent/IL259758A/en
Priority to US17/094,004 priority patent/US20210053043A1/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B01J31/2278—Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/226—Sulfur, e.g. thiocarbamates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B01J31/2269—Heterocyclic carbenes
    • B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
    • C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
    • C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
    • C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
    • C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
    • C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
    • C07C6/06—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond at a cyclic carbon-to-carbon double bond
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/54—Metathesis reactions, e.g. olefin metathesis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/54—Metathesis reactions, e.g. olefin metathesis
    • B01J2231/543—Metathesis reactions, e.g. olefin metathesis alkene metathesis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/821—Ruthenium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/22—Organic complexes

Definitions

  • This invention relates generally to metathesis catalysts and the use of such catalysts in the metathesis of olefins and olefin compounds, more particularly, in the use of such catalysts in Z or E selective olefin metathesis reactions, particularly Z or E selective cross metathesis reactions.
  • the invention has utility in the fields of organometallics and organic synthesis.
  • transition-metal catalyzed olefin metathesis reaction is an important methodology for the construction of new carbon-carbon double bonds (see (a) Fiirstner, A. Angew. Chem., Int. Ed. 2000, 39, 3013. (b) Trnka, T. M; Grubbs, R. H. Acc. Chem. Res. 2001, 34, 18. (c) Schrock, R. R. Chem. Rev. 2002, 102, 145. (d) Schrock, R. R.; Hoveyda, A. H. Angew. Chem., Int. Ed. 2003, 42, 4592. (e) Vougioukalakis, G; Grubbs, R. H. Chem. Rev. 2009, 110, 1746. (f)
  • CM cross metathesis
  • the invention provides a compound of Formula (I):
  • X is O or S
  • Y is O or S
  • Z is N or CR 32 ;
  • W is O, R 33 or S
  • R 1 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - R 27 R 28 , N0 2 , -CF3, -S(0)mR 29 , -P(0)(OH)2, -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 2 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkenyl or together with R 3 may form a polycyclic ring;
  • R 3 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl or together with R 2 may form a polycyclic ring;
  • R 4 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - R 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 5 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH)2, -OP(0)(OH) 2> -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 6 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 7 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 8 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , - ⁇ (0)( ⁇ )2, -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 9 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH)2, -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 10 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 11 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optional
  • R 12 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 13 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH)2, -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 14 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH)2, -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 15 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl, or together with R 16 may form an optionally substituted polycyclic ring;
  • R 16 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , - ⁇ (0)( ⁇ )2, -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cyclo
  • R 20 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2> -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 21 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH)2, -OP(0)(OH) 2> -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 22 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 23 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 24 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , - ⁇ (0)( ⁇ )2, -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 25 is OH, OR 30 , NR 27 R 28 , optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl,
  • R 26 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 28 is H, optionally substituted Ci-8 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 29 is hydrogen, optionally substituted Ci-24 alkyl, OR 26 , - R 27 R 28 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 30 is optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 31 is hydrogen, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 32 is hydrogen, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 33 is hydrogen, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • n 1 or 2.
  • the invention provides a method for performing a cross metathesis reaction, comprising: contacting a first internal olefin reactant with a second internal olefin reactant in the presence of a compound of Formula (I), under conditions effective to promote the formation of at least one cross metathesis product, where the first internal olefin reactant and the second internal olefin reactant may be the same or different, where the first internal olefin reactant and the second internal olefin reactant are each in a Z-configuration; and where the at least one cross metathesis product is greater than about 80% Z.
  • the invention provides a method for performing a cross metathesis reaction, comprising: contacting a first internal olefin reactant with a second internal olefin reactant in the presence of a compound of Formula (I), under conditions effective to promote the formation of at least one cross metathesis product, where the first internal olefin reactant and the second internal olefin reactant may be the same or different, where the first internal olefin reactant and the second internal olefin reactant are each in a Z-configuration; and where the at least one cross metathesis product is greater than about 90% Z.
  • the invention provides a method for performing a cross metathesis reaction, comprising: contacting a first internal olefin reactant with a second internal olefin reactant in the presence of a compound of Formula (I), under conditions effective to promote the formation of at least one cross metathesis product, where the first internal olefin reactant and the second internal olefin reactant may be the same or different, where the first internal olefin reactant and the second internal olefin reactant are each in a Z-configuration; and where the at least one cross metathesis product is greater than about 95% Z.
  • the invention provides a method for performing a cross metathesis reaction, comprising: contacting a first internal olefin reactant with a second internal olefin reactant in the presence of a compound of Formula (I), under conditions effective to promote the formation of at least one cross metathesis product, where the first internal olefin reactant and the second internal olefin reactant may be the same or different, where the first internal olefin reactant and the second internal olefin reactant are each in a Z-configuration; and where the at least one cross metathesis product is greater than about 99% Z.
  • the invention provides a method for performing a cross metathesis reaction, comprising: contacting a first internal olefin reactant with a second internal olefin reactant in the presence of a compound of Formula (I), under conditions effective to promote the formation of at least one cross metathesis product, where the first internal olefin reactant and the second internal olefin reactant may be the same or different, where the first internal olefin reactant and the second internal olefin reactant are each in an i -configuration; and where the at least one cross metathesis product is greater than about 80% E.
  • the invention provides a method for performing a cross metathesis reaction, comprising: contacting a first internal olefin reactant with a second internal olefin reactant in the presence of a compound of Formula (I), under conditions effective to promote the formation of at least one cross metathesis product, where the first internal olefin reactant and the second internal olefin reactant may be the same or different, where the first internal olefin reactant and the second internal olefin reactant are each in an -configuration; and where the at least one cross metathesis product is greater than about 90% E.
  • the invention provides a method for performing a cross metathesis reaction, comprising: contacting a first internal olefin reactant with a second internal olefin reactant in the presence of a compound of Formula (I), under conditions effective to promote the formation of at least one cross metathesis product, where the first internal olefin reactant and the second internal olefin reactant may be the same or different, where the first internal olefin reactant and the second internal olefin reactant are each in an -configuration; and where the at least one cross metathesis product is greater than about 95% E.
  • the invention provides a method for performing a cross metathesis reaction, comprising: contacting a first internal olefin reactant with a second internal olefin reactant in the presence of a compound of Formula (I), under conditions effective to promote the formation of at least one cross metathesis product, where the first internal olefin reactant and the second internal olefin reactant may be the same or different, where the first internal olefin reactant and the second internal olefin reactant are each in an -configuration; and where the at least one cross metathesis product is greater than about 99% E.
  • the invention provides a method for performing a cross metathesis reaction, comprising: contacting a first internal olefin reactant with a second terminal olefin reactant in the presence of a compound of Formula (I), under conditions effective to promote the formation of at least one cross metathesis product, where the first internal olefin reactant is in a Z-configuration; and where the at least one cross metathesis product is greater than about 80% Z.
  • the invention provides a method for performing a cross metathesis reaction, comprising: contacting a first internal olefin reactant with a second terminal olefin reactant in the presence of a compound of Formula (I), under conditions effective to promote the formation of at least one cross metathesis product, where the first internal olefin reactant is in a Z-configuration; and where the at least one cross metathesis product is greater than about 90% Z.
  • the invention provides a method for performing a cross metathesis reaction, comprising: contacting a first internal olefin reactant with a second terminal olefin reactant in the presence of a compound of Formula (I), under conditions effective to promote the formation of at least one cross metathesis product, where the first internal olefin reactant is in a Z-configuration; and where the at least one cross metathesis product is greater than about 95% Z.
  • the invention provides a method for performing a cross metathesis reaction, comprising: contacting a first internal olefin reactant with a second terminal olefin reactant in the presence of a compound of Formula (I), under conditions effective to promote the formation of at least one cross metathesis product, where the first internal olefin reactant is in a Z-configuration; and where the at least one cross metathesis product is greater than about 99% Z.
  • the invention provides a method for performing a cross metathesis reaction, comprising: contacting a first internal olefin reactant with a second terminal olefin reactant in the presence of a compound of Formula (I), under conditions effective to promote the formation of at least one cross metathesis product, where the first internal olefin reactant is in an -configuration; and where the at least one cross metathesis product is greater than about 80% E.
  • the invention provides a method for performing a cross metathesis reaction, comprising: contacting a first internal olefin reactant with a second terminal olefin reactant in the presence of a compound of Formula (I), under conditions effective to promote the formation of at least one cross metathesis product, where the first internal olefin reactant is in an -configuration; and where the at least one cross metathesis product is greater than about 90% E.
  • the invention provides a method for performing a cross metathesis reaction, comprising: contacting a first internal olefin reactant with a second terminal olefin reactant in the presence of a compound of Formula (I), under conditions effective to promote the formation of at least one cross metathesis product, where the first internal olefin reactant is in an -configuration; and where the at least one cross metathesis product is greater than about 95% E.
  • the invention provides a method for performing a cross metathesis reaction, comprising: contacting a first internal olefin reactant with a second terminal olefin reactant in the presence of a compound of Formula (I), under conditions effective to promote the formation of at least one cross metathesis product, where the first internal olefin reactant is in an -configuration; and where the at least one cross metathesis product is greater than about 99% E.
  • the invention provides for use of a compound of Formula (I) in olefin metathesis. In one embodiment, the invention provides for use of a compound of Formula (I) in an olefin metathesis reaction. In one embodiment, the invention provides for use of a compound of Formula (I) in a Z-selective olefin metathesis reaction. In one embodiment, the invention provides for use of a compound of Formula (I) in a Z-selective cross metathesis reaction.
  • the invention provides for use of a compound of Formula (I) in olefin metathesis. In one embodiment, the invention provides for use of a compound of Formula (I) in an olefin metathesis reaction. In one embodiment, the invention provides for use of a compound of Formula (I) in an -selective olefin metathesis reaction. In one embodiment, the invention provides for use of a compound of Formula (I) in an -selective cross metathesis reaction.
  • the invention provides a method for performing a Z-selective olefin metathesis reaction. In one embodiment, the invention provides a method for performing a Z-selective cross metathesis reaction.
  • the invention provides a method for performing an E- selective olefin metathesis reaction. In one embodiment, the invention provides a method for performing an -selective cross metathesis reaction.
  • alkyl refers to a linear, branched, or cyclic saturated hydrocarbon group typically although not necessarily containing 1 to about 24 carbon atoms, preferably 1 to about 12 carbon atoms, such as methyl (Me), ethyl (Et), n-propyl (Pr or n-Pr), isopropyl (i-Pr), n-butyl (Bu or n-Bu), isobutyl (i-Bu), t-butyl (t-Bu), octyl (Oct), decyl, and the like, as well as cycloalkyl groups such as cyclopentyl (Cp), cyclohexyl (Cy) and the like.
  • alkyl groups herein contain 1 to about 8 carbon atoms.
  • the term “lower alkyl” refers to an alkyl group of 1 to 6 carbon atoms
  • the specific term “cycloalkyl” refers to a cyclic alkyl group, typically having 3 to 8, preferably 5 to 7, carbon atoms.
  • substituted alkyl refers to alkyl substituted with one or more substituent groups
  • heteroatom-containing alkyl and “heteroalkyl” refer to alkyl in which at least one carbon atom is replaced with a heteroatom.
  • the terms “alkyl” and “lower alkyl” include linear, branched, cyclic, unsubstituted, substituted, and/or heteroatom- containing alkyl and lower alkyl, respectively.
  • alkylene refers to a difunctional linear, branched, or cyclic alkyl group, where "alkyl” is as defined above.
  • alkenyl refers to a linear, branched, or cyclic hydrocarbon group of 2 to about 24 carbon atoms containing at least one double bond, such as ethenyl, n- propenyl, isopropenyl, n-butenyl, isobutenyl, octenyl, decenyl, tetradecenyl, hexadecenyl, eicosenyl, tetracosenyl, and the like.
  • Preferred alkenyl groups herein contain 2 to about 12 carbon atoms.
  • lower alkenyl refers to an alkenyl group of 2 to 6 carbon atoms
  • cycloalkenyl refers to a cyclic alkenyl group, preferably having 3 to 8 carbon atoms.
  • substituted alkenyl refers to alkenyl substituted with one or more substituent groups
  • heteroatom-containing alkenyl and “heteroalkenyl” refer to alkenyl in which at least one carbon atom is replaced with a heteroatom. If not otherwise indicated, the terms “alkenyl” and “lower alkenyl” include linear, branched, cyclic, unsubstituted, substituted, and/or heteroatom-containing alkenyl and lower alkenyl, respectively.
  • alkenylene refers to a difunctional linear, branched, or cyclic alkenyl group, where "alkenyl” is as defined above.
  • alkynyl refers to a linear or branched hydrocarbon group of 2 to about 24 carbon atoms containing at least one triple bond, such as ethynyl, n-propynyl, and the like. Preferred alkynyl groups herein contain 2 to about 12 carbon atoms. The term “lower alkynyl” refers to an alkynyl group of 2 to 6 carbon atoms.
  • substituted alkynyl refers to alkynyl substituted with one or more substituent groups
  • heteroatom-containing alkynyl and “heteroalkynyl” refer to alkynyl in which at least one carbon atom is replaced with a heteroatom.
  • alkynyl and “lower alkynyl” include linear, branched, unsubstituted, substituted, and/or heteroatom-containing alkynyl and lower alkynyl, respectively.
  • alkynylene refers to a difunctional alkynyl group, where "alkynyl” is as defined above.
  • alkoxy refers to an alkyl group bound through a single, terminal ether linkage; that is, an "alkoxy” group may be represented as -O-alkyl where alkyl is as defined above.
  • a “lower alkoxy” group refers to an alkoxy group containing 1 to 6 carbon atoms.
  • alkenyloxy and lower alkenyloxy respectively refer to an alkenyl and lower alkenyl group bound through a single, terminal ether linkage
  • alkynyloxy and “lower alkynyloxy” respectively refer to an alkynyl and lower alkynyl group bound through a single, terminal ether linkage.
  • aryl refers to an aromatic substituent containing a single aromatic ring or multiple aromatic rings that are fused together, directly linked, or indirectly linked (such that the different aromatic rings are bound to a common group such as a methylene or ethylene moiety).
  • Preferred aryl groups contain 5 to 24 carbon atoms, and particularly preferred aryl groups contain 6 to 10 carbon atoms.
  • Exemplary aryl groups contain one aromatic ring or two fused or linked aromatic rings, e.g., phenyl (Ph), naphthyl, biphenyl, diphenylether, diphenylamine, benzophenone, phenanthryl and the like.
  • Substituted aryl refers to an aryl moiety substituted with one or more substituent groups
  • heteroatom containing aryl and “heteroaryl” refer to aryl substituents in which at least one carbon atom is replaced with a heteroatom, as will be described in further detail herein.
  • aryloxy refers to an aryl group bound through a single, terminal ether linkage, wherein "aryl” is as defined above.
  • An "aryloxy” group may be represented as -0-aryl where aryl is as defined above.
  • Preferred aryloxy groups contain 5 to 24 carbon atoms, and particularly preferred aryloxy groups contain 6 to 10 carbon atoms.
  • aryloxy groups include, without limitation, phenoxy, o-halo-phenoxy, m-halo-phenoxy, p- halo-phenoxy, o-methoxy-phenoxy, m-methoxy-phenoxy, p-methoxy-phenoxy, 2,4-dimethoxy- phenoxy, 3,4,5-trimethoxy-phenoxy, and the like.
  • alkaryl refers to an aryl group with an alkyl substituent
  • aralkyl refers to an alkyl group with an aryl substituent, wherein “aryl” and “alkyl” are as defined above.
  • Preferred alkaryl and aralkyl groups contain 6 to 24 carbon atoms, and particularly preferred alkaryl and aralkyl groups contain 6 to 16 carbon atoms.
  • Alkaryl groups include, without limitation, p-methylphenyl, 2,4-dimethylphenyl, p-cyclohexylphenyl, 2,7- dimethylnaphthyl, 7-cyclooctylnaphthyl, 3-ethyl-cyclopenta-l,4-diene, and the like.
  • aralkyl groups include, without limitation, benzyl, 2-phenyl-ethyl, 3 -phenyl -propyl, 4-phenyl- butyl, 5-phenyl-pentyl, 4-phenylcyclohexyl, 4-benzylcyclohexyl, 4-phenylcyclohexylmethyl, 4- benzylcyclohexylmethyl, and the like.
  • alkaryloxy and “aralkyloxy” refer to substituents of the formula -OR wherein R is alkaryl or aralkyl, respectively, as just defined.
  • acyl refers to substituents having the formula -(CO)-alkyl, -(CO)-aryl, - (CO)-aralkyl, -(CO)-alkaryl, -(CO)-alkenyl, or -(CO)-alkynyl
  • acyloxy refers to substituents having the formula -0(CO)-alkyl, -0(CO)-aryl, -0(CO)-aralkyl, -0(CO)-alkaryl, - 0(CO)-alkenyl, or -(CO)-alkynyl wherein "alkyl,” “aryl”, “aralkyl”, “alkaryl”, “alkenyl", and “alkynyl” are as defined above.
  • the acetoxy group (-0(CO)CH3; often abbreviated as -OAc) is a common example of an acyloxy group.
  • cyclic and ring refer to alicyclic or aromatic groups that may or may not be substituted and/or heteroatom containing, and that may be monocyclic, bicyclic, or polycyclic.
  • alicyclic is used in the conventional sense to refer to an aliphatic cyclic moiety, as opposed to an aromatic cyclic moiety, and may be monocyclic, bicyclic or polycyclic.
  • polycyclic ring refers to alicyclic or aromatic groups that may or may not be substituted and/or heteroatom containing, and that have at least two closed rings tethered, fused, linked via a single bond or bridged.
  • Polycyclic rings include without limitation naphthyl, biphenyl, phenanthryl and the like.
  • halo and “halogen” and “halide” are used in the conventional sense to refer to a fluoro, chloro, bromo, or iodo substituent.
  • Hydrocarbyl refers to univalent hydrocarbyl radicals containing 1 to about 30 carbon atoms, preferably 1 to about 24 carbon atoms, most preferably 1 to about 12 carbon atoms, including linear, branched, cyclic, saturated and unsaturated species, such as alkyl groups, alkenyl groups, alkynyl groups, aryl groups, and the like.
  • lower hydrocarbyl refers to a hydrocarbyl group of 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and the term
  • hydrocarbylene refers to a divalent hydrocarbyl moiety containing 1 to about 30 carbon atoms, preferably 1 to about 24 carbon atoms, most preferably 1 to about 12 carbon atoms, including linear, branched, cyclic, saturated and unsaturated species.
  • lower hydrocarbylene refers to a hydrocarbylene group of 1 to 6 carbon atoms.
  • Substituted hydrocarbyl refers to hydrocarbyl substituted with one or more substituent groups, and the terms "heteroatom- containing hydrocarbyl” and “heterohydrocarbyl” refer to hydrocarbyl in which at least one carbon atom is replaced with a heteroatom.
  • substituted hydrocarbylene refers to hydrocarbylene substituted with one or more substituent groups
  • heteroatom- containing hydrocarbylene and heterohydrocarbylene refer to hydrocarbylene in which at least one carbon atom is replaced with a heteroatom. Unless otherwise indicated, the term
  • hydrocarbyl and hydrocarbylene are to be interpreted as including substituted and/or heteroatom-containing hydrocarbyl and hydrocarbylene moieties, respectively.
  • heteroatom-containing refers to a hydrocarbon molecule or a hydrocarbyl molecular fragment in which one or more carbon atoms is replaced with an atom other than carbon, e.g., nitrogen, oxygen, sulfur, phosphorus or silicon, typically nitrogen, oxygen or sulfur.
  • heteroalkyl refers to an alkyl substituent that is heteroatom-containing
  • heterocyclic refers to a cyclic substituent that is heteroatom-containing
  • heteroaryl and “heteroaromatic” respectively refer to “aryl” and “aromatic” substituents that are heteroatom-containing, and the like.
  • heterocyclic group or compound may or may not be aromatic, and further that “heterocycles” may be monocyclic, bicyclic, or polycyclic as described above with respect to the term "aryl.”
  • heteroalkyl groups include without limitation alkoxyaryl, alkylsulfanyl-substituted alkyl, N-alkylated amino alkyl, and the like.
  • heteroaryl substituents include without limitation pyrrolyl, pyrrolidinyl, pyridinyl, quinolinyl, indolyl, pyrimidinyl, imidazolyl, 1,2,4-triazolyl, tetrazolyl, etc.
  • heteroatom- containing alicyclic groups include without limitation pyrrolidino, morpholino, piperazino, piperidino, etc.
  • substituted as in “substituted hydrocarbyl,” “substituted alkyl,” “substituted aryl,” and the like, as alluded to in some of the aforementioned definitions, is meant that in the hydrocarbyl, alkyl, aryl, or other moiety, at least one hydrogen atom bound to a carbon (or other) atom is replaced with one or more non-hydrogen substituents.
  • substituents include, without limitation: functional groups referred to herein as "Fn,” such as halo, hydroxyl, sulfhydryl, C1-C24 alkoxy, C2-C24 alkenyloxy, C2-C24 alkynyloxy, C5-C24 aryloxy, C6-C24 aralkyloxy, C6-C24 alkaryloxy, acyl (including C2-C24 alkylcarbonyl (-CO-alkyl) and C6-C24 arylcarbonyl (-CO-aryl)), acyloxy (-O-acyl, including C2-C24 alkylcarbonyloxy (-O-CO-alkyl) and C6-C24 arylcarbonyloxy (-O-CO-aiyl)), C2-C24 alkoxycarbonyl (-(CO)-O-alkyl), C6-C24 aryloxycarbonyl (-(CO)-aryl), halocarbonyl
  • alkyl (C 5 -C24 aryl), carbamido (- H-(CO)- H2), cyano(-C ⁇ N), cyanato (-0-C ⁇ N), thiocyanato (-S-C ⁇ N), isocyanate (-NisCisO), thioisocyanate (-NisCisS), formyl (-(CO)-H), thioformyl (- (CS)-H), amino (- H2), mono-(Ci-C24 alkyl)-substituted amino (-NH(Ci-C24 alkyl), di-(Ci-C24 alkyl)-substituted amino ((-N(Ci-C24 alkyl)2), mono-(Cs-C24 aryl)-substituted amino (- H(Cs-C24 aryl), di-(Cs-C24 aryl)-substituted amino (-N(Cs-C24 aryl)2)
  • alkylthio C5-C24 arylsulfanyl (-S-aryl; also termed “arylthio", C1-C24 alkylsulfinyl (-(SO)- alkyl), C5-C24 arylsulfinyl (-(SO)-aryl), C1-C24 alkylsulfonyl (-SC -alkyl), C1-C24
  • “functionalized” as in “functionalized hydrocarbyl,” “functionalized alkyl,” “functionalized olefin,” “functionalized cyclic olefin,” and the like, is meant that in the hydrocarbyl, alkyl, olefin, cyclic olefin, or other moiety, at least one hydrogen atom bound to a carbon (or other) atom is replaced with one or more functional groups such as those described hereinabove.
  • the term “functional group” is meant to include any functional species that is suitable for the uses described herein. In particular, as used herein, a functional group would necessarily possess the ability to react with or bond to corresponding functional groups on a substrate surface.
  • the aforementioned functional groups may, if a particular group permits, be further substituted with one or more additional functional groups or with one or more hydrocarbyl moieties such as those specifically enumerated above.
  • the above mentioned hydrocarbyl moieties may be further substituted with one or more functional groups or additional hydrocarbyl moieties such as those specifically mentioned above.
  • the above-mentioned hydrocarbyl moieties may be further substituted with one or more functional groups or additional hydrocarbyl moieties as noted above.
  • internal olefin means an olefin wherein each of the olefinic carbons (i.e., the carbons of the carbon-carbon double bond) is substituted by at least one non- hydrogen substituent.
  • the internal olefin may be di-substituted, tri-substituted, or tetra- substituted (e.g., R 1 HC is CHR 2 ; R 3 R 4 C is CHR 5 ; R 6 R 7 C is CR 8 R 9' ; where R 1' , R 2' , R 3' , R 4' , R 5 , R 6 , R 7 , R 8 , and R 9 may be the same or different and are each independently optionally substituted hydrocarbyl, optionally substituted heteroatom-containing hydrocarbyl, or a functional group).
  • terminal olefin means an olefin wherein one of the olefinic carbons (i.e., the carbons of the carbon-carbon double bond) is substituted by at least one non- hydrogen substituent and the other olefinic carbon is unsubstituted.
  • the terminal olefin may be di-substituted or mono- substituted (e.g., CH 2 is CHR 10' or CH 2 is CR 11 R 12 ; where R 10' , R 11' , and R 12 may be the same or different and are each independently optionally substituted hydrocarbyl, optionally substituted heteroatom-containing hydrocarbyl, or a functional group).
  • reactant internal olefin means an internal olefin present in an olefin compound used in a cross metathesis reaction with another olefin compound to form a cross metathesis product.
  • the "reactant internal olefin” may be di-substituted, tri-substituted, or tetra- substituted.
  • the "reactant internal olefin” may have an E-configuration or a Z- configuration.
  • product internal olefin means an internal olefin present in a cross metathesis product formed by a cross metathesis reaction, wherein each of the olefinic carbons (i.e., the carbons of the carbon-carbon double bond) of the internal olefin is substituted by at least one non-hydrogen substituent.
  • the "product internal olefin” may be di-substituted, tri- substituted, or tetra- substituted.
  • the “product internal olefin” may have an E configuration or a Z-configuration.
  • carbonyl as used herein, represents a group of formula "-C(O)-”.
  • ketone represents an organic compound having a carbonyl group linked to a carbon atom such as -C(0)R x wherein R x can be alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle as defined above.
  • esters represents an organic compound having a carbonyl group linked to a carbon atom such as -C(0)OR x wherein R x can be alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle as defined above.
  • amine as used herein, represents a group of formula "- R x R y
  • R x and R y can be the same or independently H, alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle as defined above.
  • amide represents a group of formula "-C(0) R x R y ,” wherein R x and R y can be the same or independently H, alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle as defined above.
  • R x and R y can be the same or independently H, alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle as defined above.
  • N represents a nitrogen atom
  • Functional groups may be protected in cases where the functional group interferes with the metathesis catalyst, and any of the protecting groups commonly used in the art may be employed. Acceptable protecting groups may be found, for example, in Greene et al., Protective Groups in Organic Synthesis, 3rd Ed. (New York: Wiley, 1999). Examples of protecting groups include acetals, cyclic acetals, boronate esters (boronates), cyclic boronate esters (cyclic boronates), carbonates, or the like. Examples of protecting groups include cyclic acetals or cyclic boronate esters.
  • the invention provides a compound of Formula (I):
  • X is O or S
  • Y is O or S
  • Z is N or CR 32 ;
  • W is O, R 33 or S
  • R 1 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - R 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 2 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkenyl or together with R 3 may form a polycyclic ring;
  • R 3 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl or together with R 2 may form a polycyclic ring;
  • R 4 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 5 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH)2, -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 6 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH)2, -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 7 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR , CN, - M R , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2> -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8
  • R 9 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2> -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 10 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 11 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH)2, -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 12 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 13 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 14 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , - ⁇ (0)( ⁇ )2, -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 15 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl, or together with R 16 may form an optionally substituted polycyclic ring;
  • R 16 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , - ⁇ (0)( ⁇ )2, -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cyclo
  • R 20 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , - ⁇ (0)( ⁇ )2, -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 21 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 22 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 23 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , - ⁇ (0)( ⁇ )2, -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 24 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 25 is OH, OR 30 , R 27 R 28 , optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl,
  • R 26 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 27 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 28 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 29 is hydrogen, optionally substituted Ci-24 alkyl, OR 26 , - R 27 R 28 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 30 is optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 31 is hydrogen, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 32 is hydrogen, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R is hydrogen, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl; and m is 1 or 2.
  • the invention provides a catalyst represented by Formula
  • X is O or S
  • Y is O or S
  • Z is N or CR 32 ;
  • W is O, R 33 or S
  • R 1 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - R 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH)2, -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 2 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2> -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkenyl or together with R 3 may form a polycyclic ring;
  • R 3 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl or together with R 2 may form a polycyclic ring;
  • R 4 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , - ⁇ (0)( ⁇ )2, -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 5 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 6 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 7 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - R 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 8 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH)2, -OP(0)(OH) 2> -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 9 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 10 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 11 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , - ⁇ (0)( ⁇ )2, -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 12 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH)2, -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 13 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 14 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR , CN, - R , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3
  • R 15 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 16 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 17 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH)2, -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl, or together with R 18 may form a polycyclic ring;
  • R 18 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH)2, -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl, or together with R 17 may form a polycyclic ring;
  • R 19 is hydrogen, optionally substituted Ci-24 alkyl, - C(0)R 25 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 20 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 21 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH)2, -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 22 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR , CN, - R , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8
  • R 23 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 24 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 25 is OH, OR 30 , NR 27 R 28 , optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl,
  • R 26 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 27 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 28 is H, optionally substituted Ci-8 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 29 is hydrogen, optionally substituted Ci-24 alkyl, OR 26 , - NR 27 R 28 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 30 is optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 31 is hydrogen, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 32 is hydrogen, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 33 is hydrogen, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl; and m is 1 or 2.
  • the invention provides a catalyst represented by Formula
  • X is S
  • Y is S
  • Z is N or CR 32 ;
  • W is O
  • R 1 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - R 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH)2, -OP(0)(OH)2, -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 2 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkenyl or together with R 3 may form a polycyclic ring;
  • R 3 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl or together with R 2 may form a polycyclic ring;
  • R 4 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH)2, -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 5 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - R 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted
  • R 6 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 7 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 8 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH)2, -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 9 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 10 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 11 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH)2, -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 12 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH)2, -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 13 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , - ⁇ (0)( ⁇ )2, -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 14 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH)2, -OP(0)(OH) 2> -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 15 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl, or together with R 16 may form an optionally substituted polycyclic ring;
  • R 16 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , - ⁇ (0)( ⁇ )2, -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cyclo
  • R 20 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , - ⁇ (0)( ⁇ )2, -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 21 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , - ⁇ (0)( ⁇ )2, -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 22 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH)2, -OP(0)(OH) 2> -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 23 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 24 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 25 is OH, OR 30 , NR 27 R 28 , optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl,
  • R 26 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 27 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 28 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R is hydrogen, optionally substituted Ci-24 alkyl, OR , - M R , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 30 is optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8
  • R 31 is hydrogen, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 32 is hydrogen, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl; and m is 1 or 2.
  • the invention provides a catalyst represented by Formula
  • X is S
  • Y is S
  • W is O
  • R 1 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - R 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH)2, -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 2 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , - ⁇ (0)( ⁇ )2, -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkenyl or together with R 3 may form a polycyclic ring;
  • R 3 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH)2, -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl or together with R 2 may form a polycyclic ring;
  • R 4 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - R 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optional
  • R 5 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 6 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH)2, -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 7 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH)2, -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 8 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 9 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 10 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH)2, -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 11 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 12 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 13 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH)2, -OP(0)(OH) 2> -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 14 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 15 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl, or together with R 16 may form an optionally substituted polycyclic ring;
  • R 16 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH)2, -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cyclo
  • R 20 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH)2, -OP(0)(OH) 2> -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 21 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2> -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 22 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 23 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH)2, -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 24 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 25 is OH, OR 30 , NR 27 R 28 , optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl,
  • R 26 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 28 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 29 is hydrogen, optionally substituted Ci-24 alkyl, OR 26 , - R 27 R 28 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 30 is optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 31 is hydrogen, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 32 is hydrogen, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl; and m is 1 or 2.
  • the invention provides a catalyst represented by Formula (I) wherein:
  • X is S
  • Y is S
  • Z is CR 32 ;
  • W is O
  • R 1 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - R 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH)2, -OP(0)(OH)2, -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 2 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl, optionally substituted C3-8 cycloalkenyl or together with R 3 may form a polycyclic ring;
  • R 3 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - R 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl or together with R 2 may form a polycyclic ring;
  • R 4 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 5 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH)2, -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 6 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 7 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 8 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH)2, -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 9 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH)2, -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 10 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR , CN, - R , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8
  • R 11 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 12 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 13 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH)2, -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 14 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 15 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl, or together with R 16 may form an optionally substituted polycyclic ring;
  • R 16 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH)2, -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cyclo
  • R 20 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH)2, -OP(0)(OH) 2> -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 21 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 22 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 23 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH)2, -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 24 is hydrogen, optionally substituted Ci-24 alkyl, halogen, - C(0)R 25 , - OR 26 , CN, - NR 27 R 28 , NO2, -CF3, -S(0)mR 29 , -P(0)(OH) 2 , -OP(0)(OH) 2 , -SR 31 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R is OH, OR , M R , optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl,
  • R 26 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8
  • R 27 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8
  • R 28 is H, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8
  • R 29 is hydrogen, optionally substituted Ci-24 alkyl, OR 26 , - R 27 R 28 , optionally substituted heterocycle, optionally substituted C3-8 cycloalkyl, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 30 is optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 31 is hydrogen, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl;
  • R 32 is hydrogen, optionally substituted Ci-24 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-8 cycloalkenyl; and m is 1 or 2.
  • the invention provides a catalyst represented by Formula (I) wherein: X is S; Y is S; Z is N; W is O; R 1 is hydrogen or optionally substituted Ci-8 alkyl;
  • R 2 is hydrogen or optionally substituted Ci-8 alkyl
  • R 3 is hydrogen or optionally substituted Ci-8 alkyl
  • R 4 is hydrogen or optionally substituted Ci-8 alkyl
  • R 5 is hydrogen, optionally substituted Ci-8 alkyl or halogen
  • R 6 is hydrogen, optionally substituted Ci-8 alkyl or halogen
  • R 7 is hydrogen, optionally substituted Ci-8 alkyl or halogen
  • R 8 is hydrogen, optionally substituted Ci-8 alkyl or halogen
  • R 9 is hydrogen, optionally substituted Ci-8 alkyl or halogen
  • R 10 is hydrogen, optionally substituted Ci-8 alkyl or halogen
  • R 11 is hydrogen, optionally substituted Ci-8 alkyl or halogen
  • R 12 is hydrogen, optionally substituted Ci-8 alkyl or halogen
  • R 13 is hydrogen, optionally substituted Ci-8 alkyl or halogen
  • R 14 is hydrogen, optionally substituted Ci-8 alkyl or halogen
  • R 15 is hydrogen, optional
  • the invention provides a catalyst represented by Formula (I) wherein: X is S; Y is S; Z is N; W is O; R 1 is hydrogen or optionally substituted Ci-8 alkyl; R 2 is hydrogen or optionally substituted Ci-8 alkyl; R 3 is hydrogen; R 4 is hydrogen; R 5 is hydrogen, optionally substituted Ci-8 alkyl or halogen; R 6 is hydrogen or optionally substituted Ci-8 alkyl; R 7 is hydrogen, optionally substituted Ci-8 alkyl or halogen; R 8 is hydrogen or optionally substituted Ci-8 alkyl; R 9 is hydrogen, optionally substituted Ci-8 alkyl or halogen; R 10 is hydrogen, optionally substituted Ci-8 alkyl or halogen; R 11 is hydrogen or optionally substituted Ci-8 alkyl; R 12 is hydrogen, optionally substituted Ci-8 alkyl or halogen; R 13 is hydrogen or optionally substituted Ci-8 alkyl; R 14 is hydrogen, optionally substituted Ci-8 alkyl or halogen;
  • the invention provides a catalyst represented by Formula (I) wherein: X is S; Y is S; Z is N; W is O; R 1 is hydrogen or optionally substituted Ci-8 alkyl; R 2 is hydrogen or optionally substituted Ci-8 alkyl; R 3 is hydrogen; R 4 is hydrogen; R 5 is hydrogen, optionally substituted Ci-8 alkyl or halogen; R 6 is hydrogen or optionally substituted Ci-8 alkyl; R 7 is hydrogen, optionally substituted Ci-8 alkyl or halogen; R 8 is hydrogen or optionally substituted Ci-8 alkyl; R 9 is hydrogen, optionally substituted Ci-8 alkyl or halogen; R 10 is hydrogen, optionally substituted Ci-8 alkyl or halogen; R 11 is hydrogen or optionally substituted Ci-8 alkyl; R 12 is hydrogen, optionally substituted Ci-8 alkyl or halogen; R 13 is hydrogen or optionally substituted Ci-8 alkyl; R 14 is hydrogen, optionally substituted Ci-8 alkyl or halogen;
  • R 20 is hydrogen or optionally substituted C 6 -io aryl;
  • R 21 is hydrogen;
  • R 22 is hydrogen;
  • R 23 is hydrogen; and
  • R 24 is hydrogen.
  • the invention provides a catalyst represented by Formula (I) wherein: X is S; Y is S; Z is N; W is O; R 1 is hydrogen; R 2 is hydrogen; R 3 is hydrogen; R 4 is hydrogen; R 5 is hydrogen, halogen or optionally substituted Ci-8 alkyl; R 6 is hydrogen or optionally substituted Ci-8 alkyl; R 7 is hydrogen or optionally substituted Ci-8 alkyl;
  • R 8 is hydrogen or optionally substituted Ci-8 alkyl
  • R 9 is hydrogen, halogen or optionally substituted Ci-8 alkyl
  • R 10 is hydrogen, halogen or optionally substituted Ci-8 alkyl
  • R u is hydrogen or optionally substituted Ci-8 alkyl
  • R 12 is hydrogen or optionally substituted Ci-8 alkyl
  • R 13 is hydrogen or optionally substituted Ci-8 alkyl
  • R 14 is hydrogen, halogen or optionally substituted Ci-8 alkyl
  • R 15 is hydrogen or halogen, or together with R 16 may form an optionally substituted polycyclic ring
  • R 16 is hydrogen, or together with R 15 may form an optionally substituted polycyclic ring
  • R 17 is hydrogen or together with R 18 may form an optionally substituted polycyclic ring
  • R 18 is optionally substituted C 6 -io aryl, halogen, or together with R 17 may form an optionally substituted polycyclic ring
  • R 19 is optionally substituted Ci-8 alkyl
  • R 20 is hydrogen or optionally substituted C 6 -io aryl;
  • R 21 is hydrogen;
  • R 22 is hydrogen;
  • R 23 is hydrogen; and R 24 is hydrogen.
  • the invention provides a catalyst represented by Formula (I) wherein: X is S; Y is S; Z is N; W is O; R 1 is optionally substituted Ci-8 alkyl; R 2 is optionally substituted Ci-8 alkyl; R 3 is hydrogen; R 4 is hydrogen; R 5 is halogen; R 6 is hydrogen; R 7 is halogen; R 8 is hydrogen; R 9 is halogen; R 10 is halogen; R 11 is hydrogen; R 12 is hydrogen or halogen; R 13 is hydrogen; R 14 is halogen; R 15 is halogen; R 16 is hydrogen; R 17 is hydrogen or together with R 18 forms an optionally substituted naphtyl or phenantryl ring; R 18 is halogen or together with R forms an optionally substituted naphtyl or phenantryl ring; R is optionally substituted Ci-8 alkyl; R 20 is hydrogen; R 21 is hydrogen; R 22 is hydrogen; R 23 is hydrogen; and R 24 is hydrogen.
  • Formula (I) wherein: X is S;
  • the invention provides a catalyst represented by Formula (I) wherein: X is S; Y is S; Z is N; W is O; R 1 is hydrogen; R 2 is hydrogen; R 3 is hydrogen;
  • R 4 is hydrogen; R 5 is hydrogen, F, methyl or i-Pr; R 6 is hydrogen or t-Bu; R 7 is hydrogen or methyl; R 8 is hydrogen or t-Bu; R 9 is hydrogen, F, methyl or i-Pr; R 10 is hydrogen, F, methyl or i- Pr; R 11 is hydrogen or t-Bu; R 12 is hydrogen or methyl; R 13 is hydrogen or t-Bu; R 14 is F, methyl, i-Pr or hydrogen; R 15 is hydrogen, methyl or CI, or together with R 16 forms 2-phenyl-naphthyl or phenanthryl; R 16 is hydrogen, or together with R 15 forms 2-phenyl-naphthyl or phenanthryl; R 17 is hydrogen or together with R 18 forms 2-phenyl-naphthyl, phenanthryl, or methylphenantryl; R 18 is CI, 3,5-dichloro-phenyl, phenyl, t-Bu or together
  • the invention provides a catalyst represented by Formula (I) wherein: X is S; Y is S; Z is N; W is O; R 1 is methyl; R 2 is methyl; R 3 is hydrogen; R 4 is hydrogen; R 5 is F; R 6 is hydrogen; R 7 is hydrogen or F; R 8 is hydrogen; R 9 is F; R 10 is F; R 11 is hydrogen; R 12 is hydrogen or F; R 13 is hydrogen; R 14 is F; R 15 is CI; R 16 is hydrogen; R 17 is hydrogen or together with R 18 forms naphtyl or phenanthryl; R 18 is hydrogen, CI, or together with R 17 forms naphtyl or phenanthryl; R 19 is i-Pr; R 20 is hydrogen; R 21 is hydrogen; R 22 is hydrogen; R 23 is hydrogen; and R 24 is hydrogen.
  • Formula (I) wherein: X is S; Y is S; Z is N; W is O; R 1 is methyl; R 2 is methyl; R 3 is hydrogen; R 4 is hydrogen; R 5
  • the invention provides a catalyst represented by Formula (I) wherein: X is S; Y is S; Z is N; W is O; R 1 is Me; R 2 is Me; R 3 is hydrogen; R 4 is hydrogen; R 5 is Me or F; R 6 is hydrogen; R 7 is hydrogen or F; R 8 is hydrogen; R 9 is hydrogen or F; R 10 is Me or F; R 11 is hydrogen; R 12 is hydrogen or F; R 13 is hydrogen; R 14 is hydrogen or F; R 15 is hydrogen or CI; R 16 is hydrogen; R 17 is hydrogen or together with R 18 forms naphthyl or phenantryl; R 18 is CI, phenyl or together with R 17 forms naphthyl or phenantryl; R 19 is i-Pr; R 20 is hydrogen; R 21 is hydrogen; R 22 is hydrogen; R 23 is hydrogen; and R 24 is hydrogen.
  • Formula (I) wherein: X is S; Y is S; Z is N; W is O; R 1 is Me; R 2 is Me; R 3 is hydrogen; R
  • the invention provides a catalyst represented by Formula (I) wherein: X is S; Y is S; Z is N; W is O; R 1 is hydrogen; R 2 is hydrogen; R 3 is hydrogen; R 4 is hydrogen; R 5 is Me, F or i-Pr; R 6 is hydrogen or t-Bu; R 7 is hydrogen or Me; R 8 is hydrogen or t- Bu; R 9 is hydrogen, Me, t-Bu, F or i-Pr; R 10 is hydrogen, Me, F or i-Pr; R 11 is hydrogen or t-Bu; R 12 is hydrogen or Me; R 13 is hydrogen or t-Bu; R 14 is hydrogen, Me, F or i-Pr; R 15 is hydrogen, methyl or CI, or together with R 16 forms 2-phenyl-naphthyl or phenanthryl; R 16 is hydrogen, or together with R 15 forms 2-phenyl-naphthyl or phenanthryl; R 17 is hydrogen or together with R 18 forms 2-
  • R 18 is CI, phenyl or together with R 17 form an optionally substituted naphthyl or an optionally substituted phenanthryl ring;
  • R 19 is i-Pr;
  • R 20 is hydrogen is phenyl;
  • R 21 is hydrogen;
  • R 22 is hydrogen;
  • R 23 is hydrogen; and
  • R 24 is hydrogen.
  • the invention provides a compound wherein the moiety
  • the invention provides a compound wherein the moiety
  • the invention provides a compound of Formula (I) is selected from:
  • a compound of Formula (I) is an olefin metathesis catalyst.
  • a compound of Formula (I) is a Z-selective olefin metathesis catalyst.
  • a compound of Formula (I) is an olefin metathesis catalyst.
  • a compound of Formula (I) is an -selective olefin metathesis catalyst.
  • an olefin reactant comprises a reactant internal olefin, wherein the reactant internal olefin is in a Z-configuration.
  • an olefin reactant comprises a reactant internal olefin, wherein the reactant internal olefin is di- substituted and is in a Z-configuration.
  • an olefin reactant comprising a reactant internal olefin is represented by the structure of Formula (1):
  • D 1 and D 2 are identical or are independently selected from nil, CH2, O, or S;
  • E 1 and E 2 are identical or are independently selected from hydrogen, hydrocarbyl (e.g., Ci- C20 alkyl, Cs-C2o aryl, C5-C30 aralkyl, or C5-C30 alkaryl), substituted hydrocarbyl (e.g., substituted C1-C20 alkyl, C5-C20 aryl, C5-C30 aralkyl, or C5-C30 alkaryl), heteroatom-containing hydrocarbyl (e.g., C1-C20 heteroalkyl, C5-C20 heteroaryl, heteroatom-containing C5-C30 aralkyl, or heteroatom- containing C5-C30 alkaryl), and substituted heteroatom-containing hydrocarbyl (e.g., substituted C1-C20 heteroalkyl, C5-C20 heteroaryl, heteroatom-containing C5-C30 aralkyl, or heteroatom- containing C5-C30 alkaryl) and, if substituted hydro
  • first internal olefin reactant there is a first internal olefin reactant and a second internal olefin reactant, where the first internal olefin reactant and the second internal olefin reactant may be the same or different, wherein the first internal olefin reactant and the second internal olefin reactant are each in a Z-configuration.
  • first internal olefin reactant and a second internal olefin reactant there is a first internal olefin reactant and a second internal olefin reactant, where the first internal olefin reactant and the second internal olefin reactant may be the same or different, wherein the first olefin reactant and the second olefin reactant each comprise a reactant internal olefin.
  • first internal olefin reactant and a second internal olefin reactant where the first internal olefin reactant and the second internal olefin reactant may be the same or different, wherein the first internal olefin reactant and the second internal olefin reactant each comprise a reactant internal olefin, wherein the reactant internal olefin is di-substituted and in a Z-configuration.
  • an olefin reactant comprises a reactant internal olefin, wherein the reactant internal olefin is in an i -configuration.
  • an olefin reactant comprises a reactant internal olefin, wherein the reactant internal olefin is di- substituted and is in an -configuration.
  • an olefin reactant comprising a reactant internal olefin is represented by the structure of Formula (2):
  • D 13 and D 14 are identical or are independently selected from nil, CH2, O, or S; and E 13 and E 14 are identical or are independently selected from hydrogen, hydrocarbyl (e.g., C1-C20 alkyl, C5-C20 aryl, C5-C30 aralkyl, or C5-C30 alkaryl), substituted hydrocarbyl (e.g., substituted C1-C20 alkyl, C5-C20 aryl, C5-C30 aralkyl, or C5-C30 alkaryl), heteroatom-containing hydrocarbyl (e.g., C1-C20 heteroalkyl, C5-C20 heteroaryl, heteroatom-containing C5-C30 aralkyl, or heteroatom-containing C5-C30 alkaryl), and substituted heteroatom-containing hydrocarbyl (e.g., substituted C1-C20 heteroalkyl, C5-C20 heteroaryl, heteroatom-containing C5-C30 aralkyl
  • first internal olefin reactant and a second internal olefin reactant there is a first internal olefin reactant and a second internal olefin reactant, where the first internal olefin reactant and the second internal olefin reactant may be the same or different, wherein the first internal olefin reactant and the second internal olefin reactant are each in an i -configuration.
  • first internal olefin reactant and a second internal olefin reactant where the first internal olefin reactant and the second internal olefin reactant may be the same or different, wherein the first internal olefin reactant and the second internal olefin reactant each comprise a reactant internal olefin, wherein the reactant internal olefin is di- substituted and is in an i -configuration.
  • first internal olefin reactant there is a first internal olefin reactant and a second internal olefin reactant, where the first internal olefin reactant is of Formula (2) and the second internal olefin reactant is of Formula (2), wherein the first internal olefin reactant and the second internal olefin reactant may be the same or different.
  • the second olefin reactant comprising a terminal olefin may be represented by the structure of Formula (3):
  • U a is selected from the group comprising nil, CFh, O, or S and T a is selected from the group consisting of hydrogen, hydrocarbyl (e.g., C1-C20 alkyl, C5-C 20 aryl, C5-C30 aralkyl, or C5- C3o alkaryl), substituted hydrocarbyl (e.g., substituted C1-C20 alkyl, C5-C 20 aryl, C5-C30 aralkyl, or C5-C30 alkaryl), heteroatom-containing hydrocarbyl (e.g., C1-C20 heteroalkyl, C5-C20 heteroaryl, heteroatom-containing C5-C30 aralkyl, or heteroatom-containing C5-C30 alkaryl), and substituted heteroatom-containing hydrocarbyl (e.g., substituted C1-C20 heteroalkyl, C5-C20 heteroaryl, heteroatom-containing C5-C30 aralkyl,
  • aryloxycarbonyl carboxyl, carboxylato, mercapto, formyl, C1-C20 thioester, cyano, cyanato, carbamoyl, epoxy, styrenyl, silyl, silyloxy, silanyl, siloxazanyl, boronato, boryl, or halogen, or a metal-containing or metalloid-containing group (wherein the metal may be, for example, Sn or [114]
  • there is a first internal olefin reactant and a second terminal olefin reactant wherein the first internal olefin reactant is in a Z-configuration.
  • first internal olefin reactant there is a first internal olefin reactant and a second terminal olefin reactant, where the first internal olefin reactant is of Formula (1) and the second terminal olefin reactant is of Formula (3).
  • first internal olefin reactant there is a first internal olefin reactant and a second terminal olefin reactant, where the first internal olefin reactant is of Formula (2) and the second terminal olefin reactant is of Formula (3).
  • the olefin product is at least one cross metathesis product, wherein the at least one cross metathesis product is in a Z-configuration.
  • the olefin product is at least one cross metathesis product, wherein the at least one cross metathesis product is di-substituted and is in a Z-configuration.
  • an at least one cross metathesis product comprises a product internal olefin, wherein the product internal olefin is in a Z-configuration.
  • an at least one cross metathesis product comprises a product internal olefin, wherein the product internal olefin is di-substituted and is in a Z-configuration.
  • the olefin product is at least one cross metathesis product, wherein the at least one cross metathesis product is in an i -configuration.
  • the olefin product is at least one cross metathesis product, wherein the at least one cross metathesis product is di-substituted and is in an -configuration.
  • an at least one cross metathesis product comprises a product internal olefin, wherein the product internal olefin is in an i -configuration.
  • an at least one cross metathesis product comprises a product internal olefin, wherein the product internal olefin is di-substituted and is in an -configuration.
  • the invention provides a method that produces a compound
  • a product, olefin product e.g., cross metathesis product
  • a carbon-carbon double bond e.g., a product internal olefin
  • Z:E ratio greater than about 1 : 1, greater than about 2: 1, greater than about 3 : 1, greater than about 4: 1, greater than about 5: 1, greater than about 6: 1, greater than about 7: 1, greater than about 8: 1, greater than about 9: 1, greater than about 95:5, greater than about 96:4, greater than about 97:3, greater than about 98:2, or in some cases, greater than about 99: 1.
  • about 100% of the carbon-carbon double bond produced in the metathesis reaction may have a Z configuration.
  • the Z or cis selectivity may also be expressed as a percentage of product formed (e.g., cross metathesis product).
  • the product e.g., cross metathesis product
  • the product may be greater than about 50% Z, greater than about 60%) Z, greater than about 70% Z, greater than about 80%> Z, greater than about 90% Z, greater than about 95% Z, greater than about 96% Z, greater than about 97% Z, greater than about 98% Z, greater than about 99% Z, or in some cases greater than about 99.5% Z.
  • an at least one cross metathesis product comprising a product internal olefin is represented by the structure of Formula (4):
  • D 3 and D 4 are identical or are independently selected from nil, CH 2 , O, or S;
  • E 3 and E 4 are identical or are independently selected from hydrogen, hydrocarbyl (e.g., Ci-C 2 o alkyl, Cs-C 2 o aryl, C5-C30 aralkyl, or C5-C30 alkaryl), substituted hydrocarbyl (e.g., substituted Ci-C 2 o alkyl, Cs-C 2 o aryl, C5-C30 aralkyl, or C5-C30 alkaryl), heteroatom-containing hydrocarbyl (e.g., Ci-C 2 o heteroalkyl, Cs-C 20 heteroaryl, heteroatom-containing C5-C30 aralkyl, or heteroatom-containing C5-C30 alkaryl), and substituted heteroatom-containing hydrocarbyl (e.g., substituted Ci-C 2 o heteroalkyl, Cs-C 2 o heteroaryl, heteroatom-containing C5-C30 aralkyl, or heteroatom-containing C5-C30 alkaryl
  • the invention provides a method that produces a compound
  • a product, olefin product e.g., cross metathesis product
  • a carbon-carbon double bond e.g., a product internal olefin
  • E:Z ratio greater than about 1 : 1, greater than about 2: 1, greater than about 3 : 1, greater than about 4: 1, greater than about 5: 1, greater than about 6: 1, greater than about 7: 1, greater than about 8: 1, greater than about 9: 1, greater than about 95:5, greater than about 96:4, greater than about 97:3, greater than about 98:2, or in some cases, greater than about 99: 1.
  • about 100% of the carbon-carbon double bond produced in the metathesis reaction may have an E configuration.
  • the E or trans selectivity may also be expressed as a percentage of product formed (e.g., cross metathesis product).
  • the product e.g., cross metathesis product
  • the product may be greater than about 50%> E, greater than about 60%) E, greater than about 70%> E, greater than about 80%> E, greater than about 90%> E, greater than about 95%> E, greater than about 96%> E, greater than about 97%> E, greater than about 98%> E, greater than about 99%> E, or in some cases greater than about 99.5%> E.
  • an at least one cross metathesis product comprising a product internal olefin, wherein the product internal olefin is in the -configuration
  • a cross metathesis product comprising a product internal olefin, wherein the product internal olefin is in the -configuration
  • D 19 and D 21 are identical or are independently selected from nil, CH 2 , O, or S;
  • E 19 and E 21 are identical or are independently selected from hydrogen, hydrocarbyl (e.g., Ci- C20 alkyl, Cs-C2o aryl, C5-C30 aralkyl, or C5-C30 alkaryl), substituted hydrocarbyl (e.g., substituted C1-C20 alkyl, Cs-C2o aryl, C5-C30 aralkyl, or C5-C30 alkaryl), heteroatom-containing hydrocarbyl (e.g., C1-C20 heteroalkyl, C5-C20 heteroaryl, heteroatom-containing C5-C30 aralkyl, or heteroatom-containing C5-C30 alkaryl), and substituted heteroatom-containing hydrocarbyl (e.g., substituted C1-C20 heteroalkyl, C5-C20 heteroaryl, heteroatom-containing C5-C30 aralkyl, or heteroatom-containing C5-C30 alkaryl) and, if substituted hydrocar
  • GC Methods Volatile products were analyzed using an Agilent 6850 gas chromatography (GC) instrument with a flame ionization detector (FID). The following conditions and equipment were used:
  • Method 1 Column: DB-225, 30m x 0.25mm (ID) x 0.25 ⁇ film thickness.
  • Oven temperature Starting temperature: 35 °C, hold time: 0.5 minutes.
  • Carrier gas Helium
  • Method 2 Column: HP-5, 30m x 0.25mm (ID) x 0.25 ⁇ film thickness.
  • Carrier gas Helium
  • C765 was synthesized according to the procedure described in US 2014/0371454. C765 was isolated as red/brown crystals in 97.1% yield.
  • N,iV-bis(2,4,6- trifluorophenyl)formimidamide 0.511 g, 1.68 mmol
  • 3-bromo-2-methylpropene 0.200 mL, 1.97 mmol
  • ort/zo-dichlorobenzene 4 mL
  • the reaction was heated to 120 °C for 60 h. After cooling to 0 °C the resulting precipitate was isolated by filtration and washed with hexanes (3 x 15 mL).
  • Table 2 summarizes a series of reactions where C765 (0.5 mol %) was exposed to various ratios of cis and tmns-5C ⁇ 4. While good stereoretention is attainable when isomerically pure starting material is used (entries 1 and 5), product distributions from reactions with mixtures of cis and trans-5Cl4 were complicated by the difference in reactivity of cis and trans stereoisomers.
  • Table 4 summarizes a series of reactions where C849z (500 ppm) was exposed to various ratios of cis and trans-5C ⁇ 4. Unlike C765, C849z afforded product distributions that approach theoretical, when the tra «5-5-tetradecene is considered an unreactive stereoisomer.
  • Table 6 summarizes a series of reactions where C849z (1000 ppm) was exposed to various ratios of cis and tram , -methyl-9-octadecenoate. Reactions with 80 or 100% c/s-methyl-9-octadecenoate (entries 1 and 2) afforded near theoretical product distributions after 4 hours with excellent stereoretention. Reactions conducted with an increased tram , -methyl-9-octadecenoate content (entries 3-5) afforded very little reactivity although products maintained high fidelity.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

L'invention concerne de manière générale des catalyseurs de métathèse et leur utilisation dans la métathèse d'oléfines et de composés oléfiniques, et plus particulièrement, l'utilisation de ces catalyseurs dans des réactions de métathèse d'oléfines Z et E sélectives. L'invention est utile dans les domaines de la synthèse de composés organométalliques et organiques.
PCT/US2016/065844 2015-12-10 2016-12-09 Catalyseurs de métathèse d'oléfines WO2017100585A1 (fr)

Priority Applications (11)

Application Number Priority Date Filing Date Title
US16/060,466 US10857530B2 (en) 2015-12-10 2016-12-09 Olefin metathesis catalysts
PL16873924.1T PL3386936T3 (pl) 2015-12-10 2016-12-09 Katalizatory metatezy olefin
CA3006976A CA3006976A1 (fr) 2015-12-10 2016-12-09 Catalyseurs de metathese d'olefines
EP16873924.1A EP3386936B1 (fr) 2015-12-10 2016-12-09 Catalyseurs de métathèse d'oléfines
JP2018530559A JP6882295B2 (ja) 2015-12-10 2016-12-09 オレフィンメタセシス触媒
EP24186768.8A EP4431180A2 (fr) 2015-12-10 2016-12-09 Catalyseurs de métathèse d'oléfines
MX2018006987A MX2018006987A (es) 2015-12-10 2016-12-09 Catalizadores de la metatesis de olefinas.
KR1020187019274A KR20180116238A (ko) 2015-12-10 2016-12-09 올레핀 복분해 촉매
CN201680071920.XA CN108368001B (zh) 2015-12-10 2016-12-09 烯烃复分解催化剂
IL259758A IL259758A (en) 2015-12-10 2018-06-03 Metathesis catalysts of studios
US17/094,004 US20210053043A1 (en) 2015-12-10 2020-11-10 Olefin metathesis catalysts

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US201562265575P 2015-12-10 2015-12-10
US62/265,575 2015-12-10
US201662377337P 2016-08-19 2016-08-19
US62/377,337 2016-08-19

Related Child Applications (2)

Application Number Title Priority Date Filing Date
US16/060,466 A-371-Of-International US10857530B2 (en) 2015-12-10 2016-12-09 Olefin metathesis catalysts
US17/094,004 Continuation US20210053043A1 (en) 2015-12-10 2020-11-10 Olefin metathesis catalysts

Publications (1)

Publication Number Publication Date
WO2017100585A1 true WO2017100585A1 (fr) 2017-06-15

Family

ID=59013592

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2016/065844 WO2017100585A1 (fr) 2015-12-10 2016-12-09 Catalyseurs de métathèse d'oléfines

Country Status (10)

Country Link
US (2) US10857530B2 (fr)
EP (2) EP4431180A2 (fr)
JP (3) JP6882295B2 (fr)
KR (1) KR20180116238A (fr)
CN (1) CN108368001B (fr)
CA (1) CA3006976A1 (fr)
IL (1) IL259758A (fr)
MX (1) MX2018006987A (fr)
PL (1) PL3386936T3 (fr)
WO (1) WO2017100585A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018038928A1 (fr) 2016-08-24 2018-03-01 Materia, Inc. Synthèse et caractérisation de catalyseurs de métathèse
US10688481B2 (en) * 2016-11-09 2020-06-23 Ximo Ag Ruthenium complexes useful for catalyzing metathesis reactions
JP2021513572A (ja) * 2018-02-13 2021-05-27 ユミコア・アクチエンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフトＵｍｉｃｏｒｅ ＡＧ ＆ Ｃｏ．ＫＧ メタセシス触媒の存在下におけるオレフィン誘導体の反応
JP2021523905A (ja) * 2018-05-15 2021-09-09 カリフォルニア・インスティテュート・オブ・テクノロジーＣａｌｉｆｏｒｎｉａ Ｉｎｓｔｉｔｕｔｅ Ｏｆ Ｔｅｃｈｎｏｌｏｇｙ 立体保持メタセシスによるプロスタグランジンｊ天然物の全合成
WO2023121492A1 (fr) * 2021-12-23 2023-06-29 Apeiron Synthesis S.A. Nouveaux complexes de ruthénium chélatants activés stériquement, leur procédé de préparation et leur utilisation dans des réactions de métathèse d'oléfines
WO2023135582A1 (fr) * 2022-01-17 2023-07-20 Uniwersytet Warszawski Nouveaux complexes de ruthénium stéréorétentifs, procédé de leur préparation, intermédiaires utilisés dans ce procédé et utilisation de nouveaux complexes de ruthénium stéréorétentifs dans des réactions de métathèse d'oléfines
EP4157814A4 (fr) * 2020-06-01 2024-07-10 Provivi Inc Synthèse de dérivés de phéromone par métathèse d'oléfines à sélectivité z

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10857530B2 (en) * 2015-12-10 2020-12-08 Umicore Ag & Co. Kg Olefin metathesis catalysts
CN110818564A (zh) * 2019-11-21 2020-02-21 石河子大学 一种利用不饱和脂肪酸酯制备高碳二元酸酯的方法
CN114213401B (zh) * 2021-12-15 2023-07-18 华南理工大学 氮杂卡宾类化合物及其制备方法
CN114634436B (zh) * 2022-04-08 2022-12-02 安徽泽升科技有限公司 一种含钌催化剂及其制备方法与用途

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020022741A1 (en) * 1998-09-01 2002-02-21 Pederson Richard L. Metathesis syntheses of pheromones or their components
US20020198426A1 (en) * 2001-03-30 2002-12-26 Morgan John P. Selective ring-opening cross-metathesis of cycloolefins
US20050261451A1 (en) * 2004-03-29 2005-11-24 California Institute Of Technology Latent, high-activity olefin metathesis catalysts containing an N-heterocyclic carbene ligand
US20080064891A1 (en) * 2006-07-12 2008-03-13 Lee Choon W Ring opening cross-metathesis reaction of cyclic olefins with seed oils and the like
WO2008065187A1 (fr) * 2006-11-30 2008-06-05 Ecole Nationale Superieure De Chimie De Rennes Complexes catalytiques a base de ruthenium et utilisation de tels complexes pour la metathese d'olefines
WO2009094201A2 (fr) 2008-01-25 2009-07-30 Trustees Of Boston College Catalyseurs pour des réactions de métathèse comprenant la métathèse énantiosélective d'oléfines et procédés correspondants
WO2012097379A2 (fr) 2011-01-14 2012-07-19 California Institute Of Technology Catalyseurs pour métathèse d'oléfines z-sélective et leur procédure de synthèse
WO2014093687A1 (fr) 2012-12-12 2014-06-19 California Institute Of Technology Catalyseurs de métathèse sélectifs pour z
WO2014186631A1 (fr) * 2013-05-15 2014-11-20 California Institute Of Technology Métathèse par ouverture de cycle/métathèse croisée hautement sélective et énantiosélective pour z
US20140371454A1 (en) 2013-06-12 2014-12-18 Trustees Of Boston College Catalysts for efficient z-selective metathesis
WO2018087230A1 (fr) 2016-11-09 2018-05-17 Ximo Ag Complexes de ruthénium utiles pour catalyser des réactions de métathèse

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001036368A2 (fr) * 1999-11-18 2001-05-25 Pederson Richard L Synthese de pheromones ou de leurs composants par metathese
CN101460513B (zh) * 2005-12-16 2014-08-27 马特里亚公司 有机金属钌配合物和制备四取代烯烃及其他受阻烯烃的相关方法
EP2428269A1 (fr) 2010-09-08 2012-03-14 Bergen Teknologioverføring AS Nouveaux catalyseurs de métathèse d'oléfines
SG11201408648YA (en) * 2012-06-29 2015-01-29 Apeiron Synthesis Sa Metal complexes, their application and methods of carrying out of metathesis reaction
PL400162A1 (pl) * 2012-07-27 2014-02-03 Apeiron Synthesis Spólka Z Ograniczona Odpowiedzialnoscia Nowe kompleksy rutenu, ich zastosowanie w reakcjach metatezy oraz sposób prowadzenia reakcji metatezy
US10857530B2 (en) * 2015-12-10 2020-12-08 Umicore Ag & Co. Kg Olefin metathesis catalysts

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020022741A1 (en) * 1998-09-01 2002-02-21 Pederson Richard L. Metathesis syntheses of pheromones or their components
US20020198426A1 (en) * 2001-03-30 2002-12-26 Morgan John P. Selective ring-opening cross-metathesis of cycloolefins
US20050261451A1 (en) * 2004-03-29 2005-11-24 California Institute Of Technology Latent, high-activity olefin metathesis catalysts containing an N-heterocyclic carbene ligand
US20080064891A1 (en) * 2006-07-12 2008-03-13 Lee Choon W Ring opening cross-metathesis reaction of cyclic olefins with seed oils and the like
WO2008065187A1 (fr) * 2006-11-30 2008-06-05 Ecole Nationale Superieure De Chimie De Rennes Complexes catalytiques a base de ruthenium et utilisation de tels complexes pour la metathese d'olefines
WO2009094201A2 (fr) 2008-01-25 2009-07-30 Trustees Of Boston College Catalyseurs pour des réactions de métathèse comprenant la métathèse énantiosélective d'oléfines et procédés correspondants
WO2012097379A2 (fr) 2011-01-14 2012-07-19 California Institute Of Technology Catalyseurs pour métathèse d'oléfines z-sélective et leur procédure de synthèse
WO2014093687A1 (fr) 2012-12-12 2014-06-19 California Institute Of Technology Catalyseurs de métathèse sélectifs pour z
WO2014186631A1 (fr) * 2013-05-15 2014-11-20 California Institute Of Technology Métathèse par ouverture de cycle/métathèse croisée hautement sélective et énantiosélective pour z
US20140371454A1 (en) 2013-06-12 2014-12-18 Trustees Of Boston College Catalysts for efficient z-selective metathesis
WO2014201300A1 (fr) 2013-06-12 2014-12-18 Trustees Of Boston College Catalyseurs pour une métathèse z-sélective efficace
WO2018087230A1 (fr) 2016-11-09 2018-05-17 Ximo Ag Complexes de ruthénium utiles pour catalyser des réactions de métathèse

Non-Patent Citations (18)

* Cited by examiner, † Cited by third party
Title
BINDER, J.B.RAINES, R.T., CURR. OPIN. CHEM. BIOL., vol. 12, 2008, pages 767
FLOOK, M. M.JIANG, A. J.SCHROCK, R. R.MULLER, P.HOVEYDA, A. H., J. AM. CHEM. SOC., vol. 131, 2009, pages 16630
FURSTNER, A., ANGEW. CHEM., INT. ED., vol. 39, 2000, pages 3013
GREENE ET AL.: "Protective Groups in Organic Synthesis", 1999, WILEY
GRUBBS, R. H.: "Handbook of Metathesis", 2003, WILEY-VCH
KEITZ, B. K.ENDO, K.PATEL, P. RHERBERT, M. B.GRUBBS, R. H., J. AM. CHEM. SOC., vol. 134, 2011, pages 9686
KHAN, R. K. M.TORKER, S.HOVEYDA, A. H., J. AM. CHEM. SOC., vol. 135, 2013, pages 10258
KOH, M.J.KHAN, K.M.TORKER, S.YU, M.MIKUS, M.S.HOVEYDA, A.M., NATURE, vol. 517, 2015, pages 181
LEITGEB, A.WAPPEL, J.SLUGOVC, C., POLYMER, vol. 51, 2010, pages 2927
LIU, X.BASU, A., J. ORGANOMET. CHEM., vol. 691, 2006, pages 5148
MARINESCU, S. C.SCHROCK, R. R.MULLER, P.TAKASE, M. K.HOVEYDA, A. H., ORGANOMETALLICS, vol. 30, 2011, pages 1780
MEEK, S. J.O'BRIEN, R. V.LLAVERIA, J.SCHROCK, R. RHOVEYDA, A. H., NATURE, vol. 471, 2011, pages 461
MING JOO KOH, KHAN R. KASHIF M., TORKER SEBASTIAN, YU MIAO, MIKUS MALTE S., HOVEYDA AMIR H.: "High-value alcohols and higher-oxidation-state compounds by catalytic Z-selective cross-metathesis", NATURE, vol. 517, no. 7533, London, pages 181 - 186, XP055223320, ISSN: 0028-0836, DOI: 10.1038/nature14061
SAMOJLOWICZ, C.BIENIEK, M.GRELA, K., CHEM. REV., vol. 109, 2009, pages 3708
SCHROCK, R. R., CHEM. REV., vol. 102, 2002, pages 145
SCHROCK, R. R.HOVEYDA, A. H., ANGEW. CHEM., INT. ED., vol. 42, 2003, pages 4592
SUTTHASUPA, S.SHIOTSUKI, M.SANDA, F, POLYM. J., vol. 42, 2010, pages 905
TRNKA, T. M.GRUBBS, R. H., ACC. CHEM. RES., vol. 34, 2001, pages 18

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11065609B2 (en) 2016-08-24 2021-07-20 Umicore Ag & Co. Kg Synthesis and characterization of metathesis catalysts
US11794179B2 (en) 2016-08-24 2023-10-24 Umicore Ag & Co. Kg Synthesis and characterization of metathesis catalysts
WO2018038928A1 (fr) 2016-08-24 2018-03-01 Materia, Inc. Synthèse et caractérisation de catalyseurs de métathèse
US10688481B2 (en) * 2016-11-09 2020-06-23 Ximo Ag Ruthenium complexes useful for catalyzing metathesis reactions
US11484873B2 (en) 2016-11-09 2022-11-01 Verbio Vereinigte Bioenergie Ag Ruthenium complexes useful for catalyzing metathesis reactions
JP7343529B2 (ja) 2018-02-13 2023-09-12 ユミコア・アクチエンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト メタセシス触媒の存在下におけるオレフィン誘導体の反応
JP2021513572A (ja) * 2018-02-13 2021-05-27 ユミコア・アクチエンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフトＵｍｉｃｏｒｅ ＡＧ ＆ Ｃｏ．ＫＧ メタセシス触媒の存在下におけるオレフィン誘導体の反応
US11958042B2 (en) 2018-02-13 2024-04-16 Umicore Ag & Co. Kg Reactions of olefin derivatives in the presence of metathesis catalysts
JP7368381B2 (ja) 2018-05-15 2023-10-24 カリフォルニア・インスティテュート・オブ・テクノロジー 立体保持メタセシスによるプロスタグランジンｊ天然物の全合成
US11866398B2 (en) 2018-05-15 2024-01-09 California Institute Of Technology Total synthesis of prostaglandin J natural products by stereoretentive metathesis
JP2021523905A (ja) * 2018-05-15 2021-09-09 カリフォルニア・インスティテュート・オブ・テクノロジーＣａｌｉｆｏｒｎｉａ Ｉｎｓｔｉｔｕｔｅ Ｏｆ Ｔｅｃｈｎｏｌｏｇｙ 立体保持メタセシスによるプロスタグランジンｊ天然物の全合成
EP4157814A4 (fr) * 2020-06-01 2024-07-10 Provivi Inc Synthèse de dérivés de phéromone par métathèse d'oléfines à sélectivité z
WO2023121492A1 (fr) * 2021-12-23 2023-06-29 Apeiron Synthesis S.A. Nouveaux complexes de ruthénium chélatants activés stériquement, leur procédé de préparation et leur utilisation dans des réactions de métathèse d'oléfines
WO2023135582A1 (fr) * 2022-01-17 2023-07-20 Uniwersytet Warszawski Nouveaux complexes de ruthénium stéréorétentifs, procédé de leur préparation, intermédiaires utilisés dans ce procédé et utilisation de nouveaux complexes de ruthénium stéréorétentifs dans des réactions de métathèse d'oléfines

Also Published As

Publication number Publication date
JP2023054086A (ja) 2023-04-13
JP2021080283A (ja) 2021-05-27
US20210053043A1 (en) 2021-02-25
JP6882295B2 (ja) 2021-06-02
MX2018006987A (es) 2019-05-16
JP2018538301A (ja) 2018-12-27
EP3386936B1 (fr) 2024-07-10
CN108368001B (zh) 2021-07-23
PL3386936T3 (pl) 2024-10-07
US10857530B2 (en) 2020-12-08
KR20180116238A (ko) 2018-10-24
EP4431180A2 (fr) 2024-09-18
EP3386936A4 (fr) 2019-08-07
US20180361371A1 (en) 2018-12-20
EP3386936A1 (fr) 2018-10-17
CA3006976A1 (fr) 2017-06-15
CN108368001A (zh) 2018-08-03
IL259758A (en) 2018-07-31

Similar Documents

Publication Publication Date Title
WO2017100585A1 (fr) Catalyseurs de métathèse d'oléfines
CN103402628B (zh) Z-选择性烯烃复分解催化剂及其合成步骤
US9238709B2 (en) Latent, high-activity olefin metathesis catalysts containing an N-heterocyclic carbene ligand
KR101291468B1 (ko) 양이온성 치환기를 함유하는 올레핀 복분해 반응의촉매로서의 전이 금속 카르벤 착물
JP5619724B2 (ja) 置換された骨格を有するｎ−ヘテロ環状カルベンリガンドを有するルテニウムオレフィン複分解触媒
US6613910B2 (en) One-pot synthesis of group 8 transition metal carbene complexes useful as olefin metathesis catalysts
US8703985B2 (en) Method for preparation of ruthenium-indenylidene carbene catalysts
US8519069B2 (en) Catalytic complex for olefin metathesis reactions, process for the preparation thereof and use thereof
AU2012206966A1 (en) Z-selective olefin metathesis catalysts and their synthetic procedure
EP3496855B1 (fr) Catalyseurs de métathèse
WO2020109217A2 (fr) Composés organométalliques
Widaman et al. New five-coordinate Ru (II) phosphoramidite complexes and their catalytic activity in propargylic amination reactions
EP3752494A1 (fr) Réactions de dérivés oléfiniques en présence de catalyseurs de métathèse
JP2020535116A (ja) 環状カーボネートの製造方法
CN109862963B (zh) Ru亚烷基络合物的合成与表征
JP4131074B2 (ja) ルテニウム化合物の製造方法
CN104437642B (zh) 一种用于烯烃复分解反应的催化剂及其制备方法
US20240150384A1 (en) Long shelf life stable organoruthenium complexes as (pre)catalysts for olefin metathesis
CN118221589A (zh) 一种手性1,3-戊二烯基-5-(2h)-吲唑化合物的合成方法
Benetsky et al. [(1 S)-endo]-(−)-borneol-tethered oxazoline phosphite as a P, N-bidentate ligand in palladium-catalyzed enantioselective allylic amination

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16873924

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 3006976

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 259758

Country of ref document: IL

WWE Wipo information: entry into national phase

Ref document number: MX/A/2018/006987

Country of ref document: MX

WWE Wipo information: entry into national phase

Ref document number: 2018530559

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20187019274

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 1020187019274

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 2016873924

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2016873924

Country of ref document: EP

Effective date: 20180710